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c. J. FRANKFORT'ER Jam-5 1-932; radczss 0F TREATINGHYDROCARBONS Re 18318 Original Filed Aug. 27, 1929 gmmto'a Reissuecl Jan. 5, 1932 UNITED STATES PATENT; OFFICE CLARENCE J. FR-ANKFORTER, OF LINCOLN, NEBRASKA, ASSIG-NOR TO FRANKFORTEB OIL PROCESS, ING., OF OMIAHA, NEBRASKA, CORPORATION OF NEBRASKA I 'rnocnss or TREATING HYDnooARBons Original No. 1,780,873, dated November 4, 1930, Serial No. 388,646, filed August 27,

- reissue filed June 16, 1931.

This invention relates to improvements in process and apparatus for treating mineral oils and heavy portions thereof, as well as lighter distillates and fractions, also hydrocarbons from shales and other sources.

The invention has for its object to facilitate the usual distillation or cracking of crudes and distillates and to do so in a manner which will increase the speed of the treatment, and result in an increased yield of the various lighter products, such as gasoline and kerosene, as well as the lubricating and gas oil fractions.

It is an object of the invention to carry out the process while the material under treat ment is undergoing usual distillation or cracking, and the results obtained are satisfactory with but a single distillation of the crude product or distillate.

The invention proceeds upon the principle that the hydrocarbon undergoing distillation or cracking in the still, is simultaneously subjected to the action of an'activated gas containing hydrogen.

The activation of the hydrogen or hydrogen containing gas is brought about by heating the gas in intimate contact with a catalystbefore its introduction into the oil. For

example, hydrogen gas or a gas containing hydrogen when subjected to the action of a high resistance electric heating element will be activated to such a degree that the volatilization of the lighter fractions of the crude or distillate will be rapid and complete. The high resistance wire acts as a catalyst and the hydrogen so activated has the function of rapidly combining with the sulphur and sulphur compounds present in the oil to form hydrogen sulphide gas, and also the effect of reducing or transforming the more complicated sulphur compounds into a simpler noncorrosive form, whereby they will not attack the apparatus.

Moreover, the hydrogen gas or hydrogen containing gas is passed in intimate contact with a catalyst and heated whereby the is activated. It will then upon introduction to the oil contained in the still, act to facilitate cracking and substantially eliminate and reduce the effect of sulphur, as described.

granulated Serial No. 544,916.

The electrical catalytic treatment, and the treatment with catalytic vcoated igneous material may be combined to activate and pre- 1929, Application for pare the gas with the same remarkable result,

and both processes may be utilized for a definite period, and then either of them may be selectively employed according tocondition, such as nature of the oil, apparatus employed,

and the products which it is desired to obtain In the drawings: 1 Figure 1 is a diagrammatic view. Figure 2 is a similar view.

Figure 3 is a view with the steps of Figures 1 and 2 combined.

Figure a is a view similar to Figures 1, 2

and 3 with a pipe still. Figure 5 is a detail view.

Referring to Figure 1, the numeral 1 indicates a conduit of any suitable size and. nature, to which is passed hydrogen or a gas containing hydrogen, such as commercial water gas, and in fact any hydrogen containing gas having a sufficient proportion of hydrogen. duit is an enlarged tube or chamber 2. Within this chamber, there is disposed at finely igneous material of cellular structure of the general nature of pumice,

which has been coated or impregnated, orv

which'has been suitably mixedwith a catalyst, such as platinum. The granular material may vary from relatively fine powder to particles of an inch or more in order that the largest vpossible platinum surface may be exposed. Arranged below the tube 2 is a heating means 3 which may be a gas burner, electric heating coils, or any other suitable apparatus. Communicating with the chamber 2 at the other end is a conduit 4;. This conduit 4 extends into the usual still or retort 5, such as is commonly. employed for the distilling or cracking of mineral oils and distillates.

The conduit 4:, as shown, enters the still above the oil leveLindicated by dot and'dash Communicating with the con- 1 still which, as stated, may be vided with a plurality of openings, slitsor perforations 7. i

Disposed below the still 5 is a suitable furnace or other heating means 8, such as is usually associated with such apparatus. An inlet '9 .for material to be treated, and an outlet for the volatile products, as well as a draw-off outlet 11 are provided in the of any usual and accepted design. V

In practicing the process, the gas under a r suitable pressure is delivered to the conduit l and passes into the tube 2, where in the presence of heat from the burners 3, it comes in intimate contact with the catalytic agent situated in the said chamber '2 I have found that the hydrogen or the hydrogen containinggas so treated becomes activated in .a most remarkable manner, and when this gas is permitted to pass through the conduit 4 to the tube 6, it will exert a very beneficial effect upon the distilling or cracking process which the oil is undergoing, to the end that a greater yield of lighter fractions is obtained, and the efiectof the sulphurcontent is minimized.

There will be'a'tendency for the 'oil to .preach itslevel in the conduit, andsinee the incoming gas will be under pressure, the oil ,willbe depressed. It will, of course, bubble up as the gas bubbles downthrough the tube out through the oil by means of the openings 7 in thetubefi, and up. throughthemain body of, the oil. This gas bubbling through the .oil keeps it well stirred, and also brings fresh 011- in contact withthe incoming gas after its'catalytic treatmentand in heated conditionto the oil, that the various fractionsseparate orcom'e off quickly and completely, and'that the greater part. of the dissolved and chemically combinedsulphur con tained in the oil is changed to hydrogen sulphide, while certain other I sulphur com ,pounds are transformed into compounds which may beeasily'removedby economical present day methods.

' It will be understood that the treatment with activated hydrogen, just described, is conducted simultaneously 'with' the distillation, or cracking :processand the heated oil subjected to the chemical action of the hydrogen as wellas to its heatcomponent is caused to ,rapidlyrvolatilize, with the result that the lighter fractions and distillates are speedily taken off.

The activated hydrogen, moreover, combines with-the corrosive sulphur and sulphur compounds to render them non-corrosive.

' For instance, most of the sulphur reactswith the hydrogen and passes: off as hydrogen sulphide gas which can be easily trapped and removed from any or all of the fractions by washing-or treatment with caustic soda;

' The effect of thehydrogen is,.m'oreover,

to reactand combine with various sulphur compounds contained in the oil to change their chemical form and destroy their well known corrosive characteristics. This is particularly true with respect to the fractions and residue remaining after the lighter frtctions and sulphur gases have been taken 0 The lighter fractions during the treatment are taken off through the outlet lO'and suitably condensed in the usual manner.

In referring to the use of an igneous material, it willbe understood that any material which has the property of readily acquiring and retaining high temperatures can be employed, and while pumice has been spe-. cifically mentioned. any other suitable material may be impregnated, coated or mixed with a catalyst. Platinum has been'specifically referred :to "as the catalyst, but there are, of course, numerous other catalyticsubstances whichwill be equally effective.

In the treatment just described, the hy drogen is activated exteriorly of the still'and supplied thereto in heated condition. The temperature to which" the hydrogen is subected in contact with the catalyst maybe varied in accordance with the oil under treatment, and the products'to be obtained, and likewise its temperature when introduced into theoil may vary withinwide limits. It is essential, however, that the temperature be such as to facilitate distillation or breaking off of the lighter fractions, and at the same time permit the hydrogen to attack and combine with the sulphur and sulphur compounds to produce sulphur gases, such as hydrogen sulphide and simpler non-corrosive compounds. i r r I have also found that if the hydrogen gas is subjected to treatment in the presence of an electric heating element, that this element will exert a catalytic action, and to an even more remarkable de ree activate the hydrogento obtain the desired results.

Referring to Figure 2, I employ astill sim-,

ilar to that previously described. A conduit 2 receives the gas or hydrogen containing gas and enters the still above the oil level therein,

as previously described, and extends downwardlv and is either integral with or has attached to it atube similar to the tube 6 previously referred to.

In Figure 2, the tube 6 is preferably formed of electrically non-conductive material, although as with. the tube shown in Figure 1,

it is heat conductive.

. The tube 6 may be formed of iron, steel, or other metal or alloy suitably coated with an electrically non-conducting material, such as glass, porcelain or other similar material.

The tube6 in Figure 2 and the leg of the conduit with which it communicates, are pro vided with an electric resistance element 'dicated at 12. It will be observed-that the resistance element extends above the level of the oil at the inlet side of the gas conduit, and

suitably insulated leads connect at-opposite ends to the resistance element, said leads being numbered 13 and 14.

The tube 6, as shown in Figure 2, is provided with similar openings, slits or perforations to those indicated in Figure l, and the end of the tube is-closed, except in so far as is necessary to permit connectionifrom the lead 14 with the resistance element. I The resistance coil is of spiral coil formation for the major portion of its length, as shown, and extends within the conduit, as well as the tube 6. It may extend throughout the entire length of the conduit or tube, ormay be of the length substantially as shown. It is desirable to allow for sufficient contact of the gas and wire to activate the gas before it contacts with the oil.

The hydrogen gas passing through the conduit comes in contact with the heated resist-- ance element, which is preferably of nickel chromium wire, anda catalytic action takes place whereby the hydrogen is activated to a very remarkable degree, and exerts even. n. ore completely its effect of speeding the complete breaking up of the lighter fractions, as well as combining with the sulphur and sulphur compounds to eliminatetheir corrosive character. It will be understood that the hydrgen or hydrogen containing gas first comes in contact with the hot wire alone, and then is in troduced into the oil while both are subjected to the action of the high resistance element, it being understood that the oil willenter the tube throughthe openings and tend to rise in the conduit up to its level.

Upon referring to the drawings, it will be seen that the tubes 6 are immersed in the oil and are disposed a sufiicient distance above the bottom ofthe'still to permit the gas to bubble out through the openings in the tubes, and also permit oil to enter the tubes and conduit to its level.

Where the electric catalytic wire is employed, there will likewise be a tendency for the oil to reach its level in the conduit, With the gas coming in, the liquid will be depressed and will, of course, bubble up as the gas bubbles down through the tube and out through the oil by means of the openings in the tube, and up through the main body of the oil. This bubbling through the oil keeps it well stirred and brings fresh oil into contact with the wire.

While I have illustrated diagrammatically but a single tube 6, it will be understood that any number of such tubes may be employed and connected to a suitable header for selectively supplying gas to any or all of such tubes. as for instance, shown in Figure 5.

Referring again to Figure 2, a suitable rheostat may be employed to regulate the temperature of the electric heating element, and While I have indicated the electric heating element as of high resistancematerial, such as nickel chromium, it will be understood that other compositions or types of electrical elements will be found satisfactory.

Referring to Figure 3, I have illustrated an apparatus wherein both catalytic treatments the other.

I have found that where the hydrogen is activated in the presence of the high resistance element, as shown in Figure 2, that for a given temperature the yield of lighter fractions and the speed of distillation is much greater than where the hydrogen is simply" passed over the pumice impregnated with platinum and then introduced into the oil. In other words, theelect'rical treatment is by far the more effective, although both treatments rely upon catalytic phenomena for their success.

' In Figure 3, it will be noted that the granularcatalyst is heated from the same source as the still, which expedient may readily be employed in the interests of fuel economy. This, of course, is not essential but indicates that if found preferable it can be resorted to. here the granular catalystic material is not disposed in the furnace or adjacent the burner, as shown in Figure 3, and it is desired to use the heat of the furnace gases, they may be piped to the'chamber by a suitable cut off, so that the chamber and its contained material will be similarly heated. Again, it may be found desirable to have both means for catalytically treating the hydrogen associated with the still with separate conduits for conveying the hydrogen into the oil.

InFigure 4;, I have illustrated'the invention applied to the commonly identified type of pipe still; Either catalytic treatment or both may be employed in themanner heretoforedescribcd, and it is preferable that the gas be introduced at two. or more points of the still. In other words, two or more tubes 6"are utilized and are positioned in the branches of the still, so that they are submerged in the oil. r I 'It is understood that the treatment with activated hydrogen is carried on concom- "mittantly with the usual distillation or observe that the speed of distillation or crack- --in g is increased, and the corrosive effect I usually associated with sulphur contained .in "oils'is eliminated.

The sulphur for the most partis combined with thehydrogen to produce hydrogen sulphide Whichpasses off with the volatiles, and is trapped and eliminated as by a washing with caustic soda.

In-addition to the hydrogen sulphide gas, the more complicated sulphur compounds are destroyed or transformed by the activated hydrogen into simpler sulphur compounds which can be economically extracted from "anvand all of the fractions. 7 i

In carrying out one test of the present in- '15 =vention, a'-crudeand a heavy distillate each containing approximately two and one-half :(2 tothree per cent of sulphur were -each'treated, audit was found that substantially two-thirds of the sulphur passed ofi'and was eliminated as hydrogen sulphide gas. I r r In another test on a high sulphur crude, substantially-three fourths 4) of the total sulphur was eliminated as hydrogen sulphide. Fixed gas'is produced during thetreatment which is slightly in excess of that produced in :ordinary: topping or skimming distilla- :tions, but not in great excess, and in fact bedistillation processes; The fixed gases should be compressed and refrigerated to recover any condensablehydrocarbons, such as go to make .up .a. light or wild gasoline comparable to any natural gas gasoline or so-called casing Qhead gasoline; The non-condensable gases are available for-fuel, for oxidation with the production of alcohols, aldehydes, etc. as is beingaccomplished to-day, or for chlorination with'theproduction of various hydrocar- ,bon chlorine compounds which 'in turn are after hydrolysed to yield various alcohols after a well known and accepted procedure.

It will be observed thatwhere the elecgric or hot wire is employed, that a rheostat "1 is inserted in the circuit so. as to regulate and controlthe temperature of the wire.

The temperature at which the hydrogen gas isintroduced into the oil will, of course, vary, as stated, but will never be below that ofthe oil in the still.

- The heat of'the gas is naturally imparted I .to the oil to assist the cracking and distillation, and since the gas is activated, its chemicalcombining powers are greatly increased, so that its effect upon the sulphur andsulphur compounds is very rapid and'at times immediate. V The gas can be continuously supplied to the oil and bubble through it or an intermittent bubbling canbe'accomplished, as desired, depending'upon the oil under treatment andother conditions.

The present invention aims to increase the proportions of the lighter fractions which nmy be obtained from a'crude' oilsor heavy ,low that produced by various cracking and portionst'hereof,andtoeliminate sulphur and the corrosive efiect of sulphur and sulphur compounds upon the ap aratus which has always been a serious pro lem. The invention greatlyincreasesthe yield of gasoline,-keroother light fractions obtainable from crude oil or heavyfractionsthereof, andin a single distillation.

The invention, as stated,ieliminates in the i form of hydrogen sulphide gas, a very large proportion of all forms of sulphur present in the hydrocarbon mixture under treatment, and changes the sulphur and sulphur compounds which may remain in the several fractions and residue of the oil to render themnon-corrosive.

It will he -understood that the-tubes or conduits for conveying the activated gas may be various sizes, and as shown in Figure 5,

there may-be any number of perforated tubes connected .to-a suitable header. Such tubes may each contain an electric resistance element, or may simply follow the embodiment 3:00

of Figure 1. In'any case,each tube will be controlled by a valve so that the amount of gas which is bubbled in contact with the oil is selectively controlled.

The tubes and conduits, 'of course, may be of various sizes, depending upon the size of the operation, the nature of the oil, and other conditions. a i

The diameter of the resistancewire may vary within fairly wide limits. .While I have and the size and capacity of the still will governthe' number of tubes employed. The tubes are preferably placed a slight distance abovethe bottom of the still so that gas may bubbletherefrom and oil may enter the tube and conduit.

Copper'leads 13 and 14 carry the required electrical energy to i the resistance wire through suitable insulating connections inthe walls of the still or othervessel, or the walls of-a tube in'a tube still.

- In Figure 2, it will be understood that the hot wire extends above the level of the oil and within the conduit, so that the gas is initially treated solely in the presence of the hot wire, and thereafter bubbles into the oil whichrhas risen in the conduit,'and is present :intthe tube6,-'so thatboth the oil'andthe gas sene, of lubricating and gas oil distillates and are simultaneously subjected to the catalytic action of the hot wire.

Since there are no perforations in the conduit above the oil level, all of the activated gas passes into and through the oil, whether the electric hot wire is used or if it is omitted. It will be understood that the tube 6 is preferably closed at its immersed end, and as stated in connection with Figure 2, only a sufficient opening is permitted to allow the electrical connections to be made.

In connection with the pipe still illustrated in Figure 4, it is well to introduce the activated hydrogen at more than one point in the cycle through the pipe still. The electrically non-conducting tube or tubes 6 carrying the resistance wires are located concentrically in one or more sections of the tubes or pipes of the still. The connections are inserted in the pipe still, preferably at points in the tubes or pipes where the oil has been thoroughly preheated. The action of the invention in connection with a still of this character is similar to that witha retort of the shell type, or any other intermittently or semi-continuously operating still.

The condensing apparatus for recovering and condensing the volatiles can be of any conventional design, as is well known.

It will be understood that the condensable, as well .as the non-condensable volatiles will carry a considerable proportion of hydrogen sulphide gas formed by the chemical interaction of the activated gas upon the sulphur and sulphur compounds in the oil under treatment. By a suitable washing as with caustic soda, the hydrogen sulphide may be eliminated, and, of course, the gases may be passed through any solution with which hydrogen sulphide reacts so as to remove it and allow the residual gases to be collected and employed as desired.

The pressure required for propelling the activated hydrogen into the still and causing it to bubble through the oil will, in most instances, not be very great, but if necessary, forcing means of any conventional type may be employed to impart to the gas a sufiicient pressure tocause it to be thoroughly introduced in contact with the oil.

It is to be understood that in treating the various hydrocarbon mixtures with the activated hydrogen obtained by the catalytic treatment described, that there results a chemical change of the actively corrosive sulphur and sulphur compounds into forms with no corrosive action upon the metal parts of the refinery equipment. This is true with respect to the various fractions distilled off, as

well as residualportions'remaining in theretort passing through. a still tube or drawn from the bottom of condensing or bubble towers. It is this feature of the invention, together with the greatly increased yield of fractions and distillates obtained which renders the process herein set forth economical and highly adaptable to the commercial refining of hydrocarbons, whether they be heavy crudes and portions thereof or various fractions.

It will be understoodthat the process illustrated and described is carried out, unlike most cracking operations, in the absence of pressure. However, it is quite possible to use my process in cracking and distilling operations where a pressure component is employed. In either case, the cracking or distillation is accomplished in the presence of the high resistance catalytic elementand the activated gas. I have found that when operating at ordinary distilling temperatures with the lighter fractions being driven oifslowly, when the activated gas, in conjunction with the electric resistance member, is employed as shown in Figures 2 and 3, that without raising the furnace temperature, the various lighter fractions aremuch more rapidly driven off and a greatly increased yield of lighter fractions obtained. 'In other words, a test of aheavy crude treated in a retort by the ordinary methods at temperatures ranging from that of initial distillation up to 450 F. the lighter fractions were driven off very slowly. Upon, however, sub

jecting the same quantity of oil and of the same character to a similar treatment, but in the presence of the hydrogen gas and the electric catalytic member, the lighter fractions are driven off much more rapidly and in larger volume, although'the temperature of the retort was not raised.

This was further proved bytreating a quantity of oil in a retort without utilizing the process of this invention when it was found that the lighter fractions distilled off slowly and to a relatively small degree. The

residue, however, when similarly treated in the presence of thehydrogen' gas and the catalytic member displayed the'remarkable e'ii'ect of additional lighter fractions rapidly splittingofl' in large volume, although thetemperature of the retort or still was not increased.

In other words, the activated gas catalytically treated and in the presence ofthe'catalytic member shown in Figures'2'and 3 exerts a cracking function upon the oil.

Referring'to Figures 2 and 3, the length of the wire and its diameter will be governed by the following conditions v I 1. The size and capacity of the still of any type. v I 2-. The temperature required for the oil under treatment and the products taken oif. Obviously a wire sufficiently. heavy for a temperature of 1500 F. would serve well at temperatures below this point, but, a wire only suflicient for a temperature of 1009? F.

would notservev well at temperatures much higher than 1000 F.

3. The electrical properties of the wire, its resistance, etc. which properties govern the current demands and resulting temperatures? In connection with the granular material employed, and which is coatedwith a catalyst, it will be understood that the material should not be too fine, since too much real fine material will offer an objectionable resistance to the gas flow. It is desired that the portions of crushedpumice or other granular material shall be of varying size so that voids may not be present in excessive amount. At the, same time the maximum amount of surface over which-the catalyst isspread is desired. 7

-Referring to the use of activated hydrogen produced either by contact with the pumice m, catalytically treated or the catalytic hot wire method, or a combination of the two,it will be understood that the hydrogen so treated may be used in continuous distillations in a pipe or tube still. I

in a retort type of still which is being oper-- ated semi-continuously or by I the batch method. 7

. The time of treatment, that is, the length of time'th'e activated gas is passing through governed by the following factors 1. The chemical nature of the hydrocarbon types or series present in the crude oil or other hydrocarbon mixture being treated.

2. The physical nature of the crude oil or other hydrocarbon mixture,that is, the proportions of gasoline, kerosene, distillate, lubricating fractions, fuel oil, etc., naturally present in the stock being. treated. v

3. The products desired by the refinery operating the process. Itmay be advisable or desirable to treat fora relatively long period of] time thus cracking and desulphurizing practically the entire charge in the; retort.

g 011- the other-hand, it may be advisable or desirable to make onlya short treatment if only the lighter. fractions of the stock in hand are desired.

In a tube or pipe still operating under'a constant pressure and therefore constant throughputfof stock, the time factor, is not readily controlled. In this case the amount of hydrogeuwouldbe controlled by using one or more gas induction. tubes. perature of the incoming activated gas would be controlled by varying the temperature of the pumice or hot wire or both. These variations in the amount and temperature of the incoming gas would, of course, vary the Ti amount of cracking and desulphurizing.

4. The amount of sulphur and sulphur compounds present in the stock treatment will govern the temperature to which the activat ed gas isfheated. Likewise, the sulphur and sulphur compound content will govern the .phur compounds present.

Moreover, it may be used the distilling hydrocarbon mixture, will be The'tem- Likewise, the period of exposure of the oil to treatment with the activated gas will depend upon the quantity of sulphur and sullarge, a longer period of treatment will be required, and if the sulphur and sulphur compound content is low, a decreased period of treatment will be employed.

Generally speaking, the treatment would continue until a test of the evolved gases and vapors showed no more than a trace of hydrogen sul hide. In some instances, I have had a fina small amount ofgreasy, cokelike residue left behind when theprocess was run until practically all of the. original charge of high sulphur West Texas crude oil was distilled over. It might be desirable in some cases to merely top a. crude known to have a relatively small proportion of gasoline and a large proportion of residue of no value save for fuel.

The volume of gas required will, of course, be dependent upon several factors, namely I v 1. The chemical nature of the naturally occurring series or types of hydrocarbons in the oil stock under treatment.

2. The chemical nature of the sulphur and sulphur compounds in the stock being treated.

3. The proportion of hydrogen in the gas being activated.

4. The desire of the refinery as to sulphur tolerances in the products being prepared.

With respect to the ratio of gas used to oil, I have found that the amount of gas required is relatively small. A fair estimate would be approximately three hundred cubic feet of commercial water gas per barrel of high sulphur West Texas crude oil. Some oils will require only a small amount of gas, the

others may require relatively large amounts. The fact that all gases coming from the stills may be used as fuel or chemically processed, prevents the use of a large amount of gas becoming an unduly large expense item in the operation of the process, even if the process did not possess other exceedingly valuable j .observed. At still higher temperature the action is yet more rapid. There is" no uesi.

tion but that thelhighertemperatures o the pumice treated catalyst increases the gas If the content is;

reactivity. It does this not only by increaslng the gas temperature, but, the hotter the catalyst, the greater the activation of the gas,

' ment may range from a temperature as low wire up temperature of 1800 F but such reaction or thermo-chemical decomposition.

up to the theoretical one hundred percent activation. The exact chemico-mechanism of gas activation is, of course, not entirely known. It is a question of molecular and atomic structural disturbances which in some way produces an unstable equilibrium. This unstable equilibrium is temporary and generally reversible and is known as the activated state.

The hot wire or electric catalytic ele- 750-800 F. to as high'at 1500-1600 F. Action is so slow at 900 F.- and exceedingly rapid at-150O F. It is possible to bring the a ten'iperature is, generally speaking, undesirable, since excessive cracking results. I have operated with the wire held quite steadily at 1500 F. with excellent results.

A phenomenon known as the thermionic effect is, I believe,responsible for the gas activation and for the cracking where the oil contacts with the wire. This action is additional to what might be termed a pure heat It is well known that atoms of some elements are somehow disturbed by ions liberated or shot off from hot metals. Generally, the metals must be heated at least to a visible red heat to produce much effect, and all metals do not appear to behave exactly alike under similar conditions. The electrical energy involved in heating the Wire also plays some part in activating the gas.

In lieu of the granulated pumice stone wl ich is coated, impregnated, or mixed with a catalyst, any porous, refractory, earthy material will be employed. Aluminum or alundum or a high temperature resisting fire brick will serre. The por sity is. necessary. This ,1- operty allows the platinum or other metal to be distributed over a very large surface area. The greater the surface exposed to the gas, the greater the activation, other things I being equal. Obviously, a substance must be used which does not react chemically with the catalyst, thereby destroying it.

Any catalyst may be used which has a high melting point with little or no affinity for oxygen, oxides of carbon or nitrogen or elementar y nitrogen, which gases are found in commercial water gas. Gold, irridium and even silver will be employed'instead of platinum whore desired, and in fact I may use any of the so-callcd noble metals. Platinum and platinum-group metals are readily gotten into the proper well distributed thin porous film on th surface of the pumice of other material. C 'cniium can be used provided the difficulty of locating it on the pumice can be overcome economically. In spite of its cost, platinum is one of thebest metals to use. The life of the catlyst in my process is not limited, hence there is no continued replacement of expensive material. Even if it did wear out which might conceivably happen after very- Chrome or Chromel and would have'less mechanical strength.

The wire employed I have found, as heretofore stated, acts as a catalyst, due to the thermionic effect described aided possibly to some extent by electrical disturbances. The treatment of the gas with the granular impregnated catalyst or the treatment of the gas with the energized catalyst, and the treatment of the gas and oil with the energized catalyst, will demonstrate that the fundamental results obtained are due to catalyses.

However, as heretofore stated, there is a theri'nionic effect responsible for the gas activation and for the cracking where the gas and the oil and gas contact with the energized catalytic element. Such thermionic effect is in addition to what might be termed a pure heat reaction or thermo-chemical decomposition.

VVit-h the method illustrated in Figure 1, there is less cracking than with the method illustrated in Figures 2 and 3. Apparently, the hot activated hydrogen or other gas employed does some cracking simply because it carries the heat directly against the large hydrocarbon molecules, andthis heat is hot enough, that is, the temperature is sufliciently high to cause thermo-chemical decomposi- This invention may be modified in various details without, however, departing from the scope of the appended claims.

What I claim is: I

1. The process of treatingliquid hydrocarbon oils and distillatesfcontaining sulphur and sulphur compounds, while in heated con-' dition, comprising chemically re-acting upon the sulphur and. sulphur compounds with a gas containing hydrogen preliminarily activated by contact with a heated contact substance, by presenting the activated gas to the liquid and further activating the gas in con.-

tact with a heated contact substance in the presence of the liquid to cause intimate contactof the activated gas with the sulphur and the sulphur compounds to produce chemical union therewith and to-change the major portion of said sulphur and sulphur compounds into volatile sulphides, and separating saidsulphides.

2. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition and in a continuously flowing body, comprising chemically re-acting upon the sulphur and sulphur compounds with a gas containing hydrogen preliminarily activated by contact with a heated contact substance, by presenting the activated gas to the liquidand furtheractivating the gas in contact with a heated contact substance in the presence of the liquid to causeintimate contact of the activated gas with the sulphur and thesul-v phur compounds to produce chemical uniontherewith and to change the major portion of said sulphur and sulphur compounds into volatile sulphides, and separating out said sulphides. r

3. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds with a gas containing hydrogen which has been activated preliminarily by contact with an electrically heated contact substance, by presenting the activated gas to the liquid and further activating the gas by contact with an electrically heated contactsurface in the presence of the liquid to cause intimate contact of the activated gas, with the sulphur and the sulphurvcompounds to produce chemical union therewith and to change the or portion of said sulphur and sulphur compounds into volatile sulphides, and separating out said sulphides.

4. The process carbon oils and distillates containing sulphur and sulphurcompounds, while in heated condition and in a continuously flowing body,

comprising chemically acting upon the-sul-- phur and sulphur compounds with a gas containing hydrogen which has been activated preliminarily by contact with an 'elec-.

trically heated contact substance, by presenting the activated gas to the liquid and further activating the gas by contact with an "electrically heated contact surface in the presence of the liquid to cause intimate contact of the activated gas with the sulphur and the sulphur compounds to producechemical union therewith and to change the major portion of said sulphur and sulphur com pounds into volatile sulphides, and separat-= ing out said sulphides. -i

of treating liquid hydro-.

5. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion. of the oil constantly circulating to and from the body of the oil, with a gas containing hydrogen which is activated'by conditionand in a continuously flowing body,

comprising chemicallyacting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil, with a gas containing hydrogen which is activated by contact with a heated contact substance located inthe confined portion of the oil, to cause intimate contact of the activated gas with the sulphurand the sulphur compounds to produce chemical union therewith and to change the major portion of said sulphur and sulphur compounds into volatile sulphides, and separating out saidsulphides.

7 The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil with a gas containing hydrogen activated in the presence of the oilby a contact substance located in said confined portion, by presenting the gas initiallyto said portion to cause intimate contact of the activated gas with the sulphur and the sulphur compounds to produce chemical union therewithand to change the major portion of said sulphur and sulphur com contact of the activated gas with the sulphur and the sulphur compounds to produce chemical union therewith and to change the major portion of said sulphur and sulphur compounds into volatile sulphides, and separating out said sulphides. w

9. The process oftreating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil, and in the body of the oil, with a gas containing hydrogen activated by contact with a heated contact substance in the confined portion of the oil, by presenting the gas ..,ccessively to said portion and the body liquid in intimate contact with the sulphur and sulohur compounds to produce chemical union therewith and to change the major portion of the sulphur'and sulphur compounds into volatile sulphides, --and separating out said sulphides.

10. The process of treating liquid hydrocarbon oils and distilla-tes containing sulphur and sulphur compounds, while in heated condition and in a continuously flowing body,

comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil, and in the body of the oil, with a gas containing hydrogen ac- =tivated by contact with a heated contact substance in the confined portion of the oil, by presenting the gas successively to said por tion and the body liquid in intimate contact with the sulphur and sulphur compounds to produce chemical union therewith and to change the major portion of the sulphur and sulphur compounds into volatile sul )hides, and separating out said sulphides,

11. The process of treating liquid hydroca-rbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly ci"culating to and from the body of the oil, with a gas containing hydrogen which is activated by contact with an electrically heated contact substance located in the confined portion of the oil, by presenting the gas so activated to said "confinedportion in intimate contact with the sulphur and sulphur compounds to produce chemical union therewith and to change the major. portion of the sulphur and sulphur compounds into volatile sulphides, and separating out said sulphides.

12. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition and in a continuously flowing body,

. comprising chemically acting upon the sulphur compounds in a confined portion of the oil circulating to-and from the body of the oil, with a gas containing hydrogen which is activated by contact with an electrically heated contact substance located in the confined portion of the oil by presenting the gas so activated to said confined portion in intimate contact with the sulphur and sulphur compounds to produce chemical union therewith and to change the'maj or portion of the sulphur and sulphur compounds into volatile sulphides, and separating out said sulphides. 13. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body'of the oil, and in the body of the oil, with agas containing hydrogen which is activated by contact with an electrically heated contact substance located in the confined portion of the oil, by presenting the gas successively to said confined portion and the body liquid in intimatecontact with the sulphur and sulphur compounds to produce chemical union therewith and to and sulphur compounds, while in heated con-l di'tion and in a continuouslyfiowing body, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to i and from the body of the oil, and in'the body of the oil, with a gas containinghydrogen, which is activated by contact with an electrically heated contact substance located in the confined portion of the oil by presenting the gas successively to said confined portion and the body liquid in intimate contact with the sulphur and sulphur compounds to produce chemical union therewith and to. change the 1113101 portion of the sulphur and sulphur compounds into volatile sulphides, and separating out said sulphides.

15. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically. re-acting upon the sulphur and sulphur compounds with a gas containing hydrogen preliminarily activated by contact with a heated contact substance, by presenting the activated gas to the liquid and further activating the gas in contact with a heated contact substance in the presence of the liquid to cause intimate contact of the activated gas with the sulphur and the sulphur compounds to produce chemical union therewith and to change the major portion of said sulphur and sulphur compounds into volatile sulphides, and simultaneously producing pyrolysis of the oil, thereby obtaining more volatile hydrocarbons and separating out said sulphides.

' 16. The process of treating liquid hydro carbon oils and distillates containing sulphur andsulphur compounds, while in heated con- Y dition and in a continuously flowing body,

-sulphides, and simultaneously producing comprising chemically re-actingupon the sulphur and sulphur compounds with a gas containing hydrogen preliminarily activated by contact with a heated contact substance, by presenting the activated gas to the liquid and further activating the gas in contact with a heated contact substance in the presence of the liquid to cause intimate contact of the activated gas with the sulphur and sulphur compounds to produce chemical union therer with and to change the major portion of said sulphur and sulphur compounds into volatile pyrolysis of the oil, thereby obtaining more volatile hydrocarbons and separating out said sulphides. V i 17. The process of treating liquid hydro carbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds with a gas containing hydrogen which has been activated preliminarilyby'contact with an electrically heated contact substance, by presenting the activated gas to the liquid and further "activating the gas by cont-act with an electrically heated contact surface inthe presence of the liquid to cause intimate contact of the activated gas with the sulphur and the sulphur compounds to produce chemical union therewith and to change the major portion of said sulphur and sulphur compounds into volatile sulphides, and simultaneously pro- 1 ducing pyrolysis of the oil, thereby obtaining I mbreyolatile hydrocarbons and separating out thesulphides.

18. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition and in a continuously flowing body, comprising chemically acting upon the sul- .phur and-sulphur compounds with a gas con- "ta'ininghydrogen which has been activated preliminarily by contact with an electrically heated contact substance, by presenting the activated gas to the liquid and further activatingthe gas by contact with an electrically heated contactsurface in the presence of the 7 liquid to cause intimate contact of the activated gas with the sulphur and the sulphur compounds to produce chemical union therewith and to change the major portion of said sulphur and sulphur compounds into volatile sulphides, and simultaneously producing pyrolysis of the oil, thereby obtaining more volatile hydrocarbons and separating out .Isaidsulphides.

19. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while'in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil, with a gas containing hydrogen which is activated by contact with a heated contact substance located in the confined portion of the oil, to cause intimate contact voi the activated gas with the sulphur and the sulphur compounds to produce chemical union therewith and to change the major portion of said sulphur and sulphur compounds into volatile sulphides, and simultaneouslyproducing pyrolysis of the oil, thereby obtaining more volatile hydrocarbons and separating out said sulphides. V 20. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition and in a continuously flowing body,

comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil, with .a, gas containing hydrogen which is activated by contact with a heated contact substance located in the confined portion of the oil, to cause intimate contact of the activated gas with the sulphur and the sulphur compounds to produce'chemical union therewith and to change the major portion of said sulphur and sul-- phur compounds into volatile sulphides, and simultaneously producing pyrolysis of the oil, thereby obtaining morevolatile hydrocarbons and separating out said sulphides.

21. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil with agas containing hydrogen activated in the presence of the oil by a contact substance locatedin said confined portion, by presenting the gas initially to said portion to cause intimate contact of the activated gas with the sulphur and the sulphur compounds to produce chemical union therewith and to change the major portion of said sulphur and sulphur compounds into volatile'sulphides, and simultaneously producing pyrolysis of the oil, thereby obtaining more volatile hy-- drocarbons and separating out said sulphides. V

22. The process of treating liquid hydrocarbon oils and distillates containingsulphur" and sulphur compounds, whilein heated condition and in a. continuously flowing body, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil with a gas con-- taining hydrogen activated in the presence of the oil by a contact substance located in said confined portion, by presenting the gas initially to said portion to cause intimate contact of the activated gas with the sulphur and the sulphur compoundsto produce chemical union therewith and to change the major portion of said sulphur and sulphur com-.

pounds into volatile sulphides, and simultaneously producing pyrolysis of the oil, thereby obtaining more volatile hydrocarbons and separating out said sulphides.

23. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil, and in the body of the oil, with a gas containing hydrogen activated by contact with a heated contact substance in the confined portion of the oil, by presentin the gas successively to said portion and theTmdy liquid in intimate contact with the sulphur and sulphur compounds to produce chemical union therewith and to change the major portion of the sulphur and sulphur compounds into volatile sulphides, and simultaneously producing pyrolysis of the oil thereby obtaining more volatile hydrocarbons, and separating out the sulphides.

24. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated con dition and in a continuously flowing body, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil, and in the body of the oil, with a gas containing hydrogen activated by contact with a heated contact substance in the confined portion of the oil, by presenting the gas successively to said portion and the body liquid in intimate contact with the sulphur and sulphur compounds to produce chemical union therewith and 'to change the major portion of the sulphur and sulphur compounds into volatile sulphides, and simultaneously producing pyrolysis of. the oil thereby obtaining more volatile hydrocarbons, and separating out the sulphides.

25. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to and from the body of the oil, with a gas containing hydrogen which is activated by contact with an electrically heated contact substance located in the confined portion of the oil, by presenting the gas soactivated to said confined portion in intimate contact with the sulphur and sulphur compounds to produce chemical union therewith and to. change the major portion of the sulphur and sulphur compounds into volatile sulphides, and simultaneously producing pyrolysis of the oil, thereby obtaining more volatile hydrocarbons and separating out said sulphides.

26. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition and in a continuously flowing body, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil circulating to and from the body of the oil, with a gas containing hydrogen which is activated by contact with an electrically heated contact substance located in the confined portion ofthe oil by presenting the gas so activated to said confined por-V tion in intimate contact with the sulphur and sulphur compounds to produce chemical union therewith and to change the major portion of the sulphur. and sulphur compounds into volatile sulphides, and simultaneously producing pyrolysis of the oil, thereby obtaining more volatile hydrocarbons and separating out said sulphides.

27. The process of treating liquid hydrocarbon oils and dist-illates containing sulphur and sulphur compounds-while in heated condition, comprising chemically acting upon the sulphur and sulphur compounds in a confined portion of the oil constantly circulating to andfrom the body of the oil, and in the body of the oil, with a gas containing hydrogen .which is activated by contact with an electrically heated contact substance located in the confined portion of the oil, by present- I ing the gas successively to said confined porcarbon oils and disti lates containing sulphur and sulphur compounds, while in heated condition and in a continuously flowing body, comprising chemically acting upon the sulphur and sulphurcompounds in a confined portion of the oil constantly circulating to and from the body of the oil, and in the body of the oil, with a gas containing hydrogen which is activated by contact with an electrically heated contact substance located in the confined portion of the oil by presenting the gas successively to said confined portion and the body liquid in intimate contact with the sulphur and sulphur compounds to'produce chemical union therewith and to change the major portion of the sulphur and sul-' phur compounds into volatile sulphides, and simultaneously producing pyrolysis of the. oil, thereby obtaining more volatile hydrocarbons and separating out said sulphides.

29. The process of treating liquidhydrocarbon oils and distillates containing sulphur and sulphur compounds, while in heated condition, which comprises conducting to the liquid and bubbling in intimate contact with the sulphurand'sulp'hur compounds therein, a gas containing hydrogen, activating saidgas by contact through a substantial portion of itspath of travel with the exposed heated -surface of a separately heatedsolid contact substance located. in a conduit leading from a-- gas supply into'theoil, to cause said/activated gas to chemically re-act with the sul-- phur'and sulphur compounds. to produce chemical union therewith and change the major portion of said sulphurand sulphur compounds into volatile sulphides and separatingaout said sulphides/said gas being presented to the liquid'under'a relatively low pressure adapted. to effect said bubbling action. v

30. The process of treating liquid hydrocarbon oils and distillates containing sulphur and sulphur compounds while in heated condition, which comprises conducting to the liquid and bubbling in intimate contact with the sulphur and. sulphur compounds therein an activated gas containin'g hydrogen,-acti-- vating said gas by contact through a substantial portion of itsp ath of travelwithwthe f exposed heated surface of a-separatelyhea? ed contact substance comprising: a porous material located out of contactwith the oil,-

andrin a conduit leading from the gas supply tothe oil-, and causing. said activated gas to; chemically react with the sulphur and sul-m:

phur compounds to produce'chemical union therewith and change the'major portion of sai'd'sulphur and sulphur compounds into volatile sulphides and separating .outsaid sulphides, said gas being presented to the liquid under arelatively 'low pressure adapted to'effectsaid bubblinggaction. V i In testimony whereof I have hereunto set my" hand. I

an activated gas containing hydrogen, activatingsaid gas by contact through a substang 'tial portion of its pathof travel with the exposed'heated surface of a separately heated solid contact substance located out of contact with the oil and in a conduit leading from the gas supply to the oil, and causing said activated gasto chemically react with the sulphur and sulphur compounds to produce chemical union therewith and change the ma- 1' or portion of said sulphur and sulphur compounds intorvolatile sulphides and separating outasaid sulphides, saidgas being presented to the liquid under a relatively low pressure adapted to effect said bubbling action.

31. The process of treatingliquid'hydrocarbon oils and .distillates, containing sulphur and sulphurcompounds while in heated condition, which comprises conducting to the liquid and bubblingin intimate contact with the sulphur and sulphur compounds therein and activated gas containing hydrogen, acti-- vating said gas by contact through asubstantial portion of its path of travel with the exposed heated surface of a separately heated contact substance comprising an'electrical resistance located out of contact with the oil and in a conduit leading from the gas supply to the oil, and causingsaid activated gas to chemically react with the sulphur and sulphur compounds to produce chemical union therewith and change the major portion of said sulphur and sulphur compounds into volatile sulphides and separating out said sulphides, said gas being presented to the liquid under a relatively low pressure adapted to effect said bubbling action.

352.- The processof treating liquid hydrocarbon oils anddistillates,containing sulphur and sulphur compounds while in heated condition,which comprises conducting to'the liquid and bubbling intimate contact with the sulphur and'sulpliur compounds therein CLARENCE J'. raANKFonrER;

aif 

